Metal complexes of sulfoalkalated tannies



United States Patent 3,391,173 METAL COM-PLEXES 0F SULFQALK LATED TANNIN Charles A. Stratton, Copan, lrla., assigner to Phillips Petroieum Company, a corporation of Deiaware No Drawing. Originai application Sept. 30, 1965, Ser. No. 491,837, now Patent No. 3,344,663, dated Sept. 26, 1967. Divided and this application Feb. 6, 1967, Ser. No. 613399 17 Claims. ((31. 260-429) ABSTRACT OF THE DISCLOSURE Additives, suitable for use in drilling fluids, comprising a metal complex of a sulfoalkylated tannin. In one method of preparation, said additives can be prepared by inter-reacting, in an alkaline aqueous medium under suit able reaction conditions, a tannin compound such as quebracho, a carbonyl compound such as an aldehyde or ketone, and a metal compound such as an iron compound.

This application is a division of my conpending application Ser. No. 941,837, filed Sept. 30, 1965, now Patent No. 3,344,063. Said copending application was field as a continuation-in-part of then copending application Ser. No. 258,888, filed on Feb. 15, 1963, and now abondoned.

This invention relates to drilling fluids and additives therefor. In one aspect this invention relates to drilling fluids having improved water loss properties and/or improved viscosity or other rheological characteristics. In another aspect this invention relates to an additive for drilling fluids and a process for making same, which additive when incorporated in a drilling fluid imparts improved water loss properties and/or viscosity or other rheological characteristics to said drilling fluid.

In the art of drilling wells to tap subterranean deposits of fluids such as oil and/or gas, especially when drilling by the rotary method employing a rotary bit and drill stem, a drilling fluid, usually a compounded fluid made to predetermined physical and chemical properties, is circulated to the bottom of the bore hole, out through openings in the bit at the bottom of the bore hole, and then back up said bore hole to the surface by passage through the annular space between said drill stem and the wall of said bore hole (or between said drill stern and the wall of the casing where the casing has been put in place).

The drilling fluid must act as a liquid medium of controlled viscosity for removing cuttings from the bore hole; it must prevent excessive amounts of fluid from flowing from the bore hole into surrounding formations depositing on the wall of the hole a thin but substantially impervious filter cake; it must possess a gel structure of suflicient strength to hold in suspension solids, particularly during any time the fluid is not circulating; and it must and may also contain weighting materials, all suspended in the water. The nonaqueous or oil base drilling fluids normally comprise a nonaqueous liquid such as crude oil or a petroleum distillate, and a weighting material which can be a clay or other suitable material. In addition to aqueous and nonoqueous drilling fluids as defined above, emulsion-type drilling fluids are often used. These "ice emulsion drilling fluids normally comprise a substantially water-insoluble liquid such as oil, a finely divided inorganic material such as clay, and water, together with a suitable dispersing or emulsifying agent. The two types of emulsion drilling fluids are the oil-in-water emulsion type, sometimes referred to as water base emulsion type, and the water-in-oil emulsion type, sometimes referred to as oil base emulsion type. In the latter, oil forms the continuous phase of the emulsion, and in the former, water or brine forms the continuous phase of the emulsion.

In the drilling of wells there are major difficulties caused by natural formations penetrated. One of these difficulties is the encountering of certain formations, such as gypsum, which will cut the drilling mud so that the clay particles are flocculated and the viscosity becomes too high. In such instances there is danger of the drill pipe twisting in half, or of gas cutting of the mud, or of a blowout occurring due to the cutting of the mud. Another difliculty is the encountering of formations known as heaving shale. A heaving shale absorbs water from the drilling mud and by a caving or disintegrating action common to clay and shale, or by a swelling action common to bentonite materials, the well hole is closed around the drill string, choking oi the circulation of drilling mud and often seizing the drill string so that it cannot be rotated or twists in half. Another difficulty which is frequently encountered in deeper wells is gelation and/or thickening of the drilling mud due to the higher temperatures encountered in said deeper wells. In such instances the drilling mud actually gels and/or thickens, greatly increasing the pump pressures required for circulating the drilling mud. In severe cases it becomes practically impossible to properly circulate the mud. Furthermore, said high temperature gelation is frequently aggravated by the presence of contaminants such as gypsum, salt, cement, etc. in the drilling mud. Thus, another requirement for drilling muds is that they be characterized by stability at the higher temperatures encountered in deeper wells.

I have now discovered a new class of additives for drilling fluids, which additives when incorporated in aqueous drilling fluids, e.g., water base drilling fluids and oil-inwater emulsion drilling fluids, impart enhanced water loss properties and/or enhanced viscosity or other rheological characteristics to said drilling fluids. Said new additives are metal complexes of sulfoalkylated tannin.

Thus, broadly speaking, the present invention resides in said new additives; methods for preparing said new additives; drilling fluids containing one or more of said new additives; and methods of using said drilling fluids in the drilling of wells.

Thus, an object of this invention is to provide an improved drilling fluid. Another object of this invention is to provide an improved drilling fluid having enhanced water loss properties and/ or enhanced viscosity or other rheological characteristics. Another object of this invention is to provide improved aqueous drilling fluids which are characterized by stability to the high temperatures encountered in drilling deep wells. Another object of this invention is to provide new additives for use in aqueous drilling fluids, e.g., water base drilling: fluids and oil-inwater emulsion drilling fluids, which additives will impart enhanced water loss properties and/or enhanced viscosity or other rheological characteristics to said drilling fluids. Another object of this invention is to provide methods of preparing said new drilling fluid additives. Another object of this invention is to provide methods of using said improved drilling fluids in the drilling or workover of wells. 0th r aspects, objects, and advantages of the invention will be apparent to those skilled in the art in view of this disclosure.

Thus, according to the invention, there is provided an aqueous Well drilling fluid comprising: water; suflicient finely divided solids to form a filter cake on the wall of the well; and an amount of a metal complex of a sulfoalkylated tannin sufficient to reduce at least one of (a) the water loss due to filtration through said filter cake, (b) the yield point, and (c) the -minute gel, but insuflicient to increase the viscosity of said drilling fluid to such an extent that it cannot be circulated; said metal being selected from the group consisting of iron, copper, chromium, nickel, cobalt, maganese, zinc, aluminum, titanium, and vanadium.

Further according to the invention, there is provided an aqueous well drilling fluid comprising a mixture containing: water; sufiicient suspended finely divided solids to form a filter cake on the wall of the well; and an amount of a metal complex of a sulfoalkylated tannin sufiicient to reduce the water loss due to filtration through said filter cake but insuflicient to increase the viscosity of said drilling fluid to such an extent that it cannot be circulated; said metal complex having been prepared by the interreaction, in an alkaline aqueous reaction medium under reaction conditions, between a tannin compound, a carbonyl compound selected from the group consisting of the lower molecular weight aldehydes and ketones, a sulfur compound selected from the group consisting of sulfurous acid and water-soluble salts thereof, and a metal compound selected from the group consisting of the hydroxide and water-soluble salts of iron, copper, chromium, nickel, cobalt, manganese, zinc, aluminum, titanium, and vanadium.

Further according to the invention, there are provided methods of using the improved well drilling fluids of the invention, which methods comprise circulating said well drilling fluids into and from the bore hole in contact with the walls of said bore hole.

Still further according to the invention, there are provided as new compounds, metal complexes or sulfoalkylated tannins, and methods of preparing same, as discussed further hereinafter.

The metal complexes of sulfoalkylated tannins which are the new additives of the invention are preferably those which are soluble in the water phase of the drilling fluid. However, as discussed further hereinafter, the invention is not limited to the metal complexes of sulfoalkylated tannins which are completely soluble in water. It is suflicient if said metal complexes can be readily dispersed in the water phase of the drilling fluids in any suitable manner.

Examples of metal compounds which can be used in the preparation of the metal complexes of the invention, include, among others, the water-soluble salts such as the nitrate or chloride, and the hydroxides or hydrated oxides of iron, copper, chromium, nickel, cobalt, manganese, zinc, aluminum, titanium, and vanadium. Generally speaking, the water-soluble salts are preferred. However, the hydrated oxides or hydroxides of said metals are sometimes preferred compounds for use in the practice of the invention because they contain no anions such as chloride or nitrate which would be left in the reaction mixture when the cation is complexed with the tannin. Another preferred class of metal-containing compounds which can be used in the practice of the invention are the ammonium and the alkali metal salts of the above metals wherein the said above metals are present in the anion portion of the molecule, e.g., the alkali metal chromates, vanadates, titanates, manganates, etc., and the alkali metal dichromates. As used herein and in the claims, unless otherwise specified, the term alkali metal is employed generically to include sodium, potassium, lithium, rubidium, cesium, and ammonium.

Tannins which can be used in preparing the metal complexes of sulfoalkylated tannins in accordance with the invention are the vegetable tannins, including both the gallotannins and the flavotannin (sometimes called catechol tannins). Thus the word tannin as used herein and in the claims, unless otherwise specified, refers to and includes the vegetable gallotannins and the vegetable flavotannins. Examples of the gallotannis include: tannic acid or Chinese Tannin; Turkish Tannin; Hamamelis Tannin; Acer-tannin; Glucogallin; Sumac tannin; Valonia oak gall tannin; tea tannin; Tara; Myrabolam; Divi-Divi; Algarobillo; oak; and chestnut. Examples of flavotannins include: Gambier and Catechu or Burma Cutch; Quebracho; Tizerah; Urunday; Wattle; Mangrove; Spruce; Hemlock; Larch; Willow; and Avaram. Said flavotannins are the preferred tannins for use in the practice of the invention.

Quebracho is the presently most preferred tannin for use in the practice of the invention. Quebracho is extracted from the bark and wood of the quebracho tree with water. The conventional method of preparing quebracho is to disintegrate the wood and bark, extract the bark and/or wood with water, the solution of quebracho and water is evaporated to percent concentration of quebracho and the concentrated quebracho is spray dried. Quebracho is the commercial catechol tannin or flavotannin product. The high tannin content (about 20 percent) of the wood of the quebracho tree makes it the important source of catechol tannins. The principal source of gallotannins is gall nuts.

The metal complexes of sulfoalkylated tannin, either a gallotannin or a flavotannin, can be prepared by several different procedures, all in accordance with the invention. All of said procedures involve the interreaction, in an alkaline aqueous reaction medium under reaction conditions, between a tannin compound, a carbonyl compound selected from the group consisting of aldehydes and ketones, a sulfur compound selected from the group consisting of sulfurous acid and water-soluble salts thereof, and a metal compound selected from the group consisting of the hydrated oxides or hydroxides and the watersoluble salts of iron, copper, chromium, nickel, cobalt, manganese, zinc, aluminum, titanium, and vanadium. Thus, in one method in accordance with the invention, an alkali metal hydroxide, e.g., sodium hydroxide, an aldehyde or ketone, e.g., formaldehyde or acetone, a sulfite, e.g., sodium sulfite or sodium bisulfite, a tannin, e.g., quebracho (quebracho extract), and a suitable metal compound, e.g., ferric hydroxide, are added to water in a reaction vessel to form a reaction mixture. The sequence of adding said reactants to the water is not critical. However, it is sometimes preferred to add the alkali metal hydroxide first. The amount of alkali metal hydroxide employed will be an amount suflicient to make the reaction mixture alkaline, at least initially. Said reaction mixture is then maintained under conditions of time and temperature sufficient to cause the substantial conversion of the tannin compound into a metal complex of sulfoalkylated tannin.

If desired, the carbonyl compound, e.g., formaldehyde or acetone, and the sulfite can be prereacted. Thus, in one method, for example, a solution containing formaldehyde and sodium sulfite is prepared separately and then combined with the other reactants in the alkaline reaction medium.

In one preferred method for preparing the metal complexes of the invention, an alkaline first solution is prepared by dissolving a tannin (such as quebracho extract), and an alkali metal hydroxide (such as sodium hydroxide) in water. A second solution is formed by admixing a carbonyl compound (such as formaldehyde) and a sulfite (such as sodium bisulfite) in water. Said second solution is then added to said first solution to form a third solution. Said third solution is then maintained at an elevated temperature for a period of time suflicient for at least a substantial portion of said aldehyde and said sulfite to react with said tannin to form a sulfoalkylated tannin. A metal compound (such as ferric hydroxide) is then added to said third solution and reacted with the sulfoalkylated tannin therein to form a metal complex of sulfoalkylated tannin which is recovered from the resulting reaction mixture. In this instance, using the exemplary reactants mentioned above, the product is an iron complex of sulfomethylated quebracho.

In another preferred method for preparing the metal complexes of the invention, the desired amount of water is added to a reactor vessel equipped with suitable stirring means. The desired amount of carbonyl compound (such as formaldehyde) is then added to said water with stirring. The desired amount of a sulfite (such as sodium bisulfite) is then added to the water, with stirring, and the carbonyl compound and sulfite are permitted to react to completion. Usually the reaction time will be within the range of 0.5 to 3 hours and the final temperature will be in the order of 125 F., depending upon the initial ambient temperature of the water, the amount of reagents, etc. The desired amount of an alkali metal hydroxide (such as sodium hydroxide) is then added. The tannin compound (such as quebracho) is then added to the tank containing the above reagents with vigorous stirring. Heating is initiated and the solution is maintained at an elevated temperature which is preferably within the range of 180 to 200 F. for a period of from 1 to 6 hours. The desired amount of a metal compound is then added to the solution of sulfoalkylated tannin and reacted therewith to form a metal complex of sulfoalkylated tannin. It is not necessary to add additional heat to the reactant solution during the addition of the metal compound. The residual heat remaining from dissolving the tannin compound will usually be suthcient. After the sulfoalkylation reaction is complete the metal complex of sulfoalkylated tannin is recovered from the reaction solution in any suitable manner, such as by drum drying or spray drying.

If desired, the metal can be complexed with the tannin compound first. In this method, the metal compound is added to an alkaline solution of the tannin to form the metal complex of said tannin. Said metal complex is then sulfoalkylated by adding the carbonyl compound and sulfite, either prereacted or not prereacted, to the solution of the metal complex of the tannin to sulfoalkylate said metal complex and form a metal complex of sulfoalkylated tannin.

In all of the above methods for preparing the additives of the invention, the metal complexes of sulfoalkylated tannin can be recovered from the reaction mixture by any suitable method such as evaporation, drum drying, spray drying, etc. It is not essential to recover said metal complexes of sulfoalkylated tannin from the reaction mixture. Said reaction mixture can be used per se in liquid form in the drilling fluids of the invention. However, it is preferred to recover and dry said metal complex products. The dried solids can then be bagged and shipped to the field for use in the drilling muds described herein.

The vegetable tannins are high molecular weight materials having molecules of complex structure containing phenolic hydroxyl groups. Some authorities consider said tannins to be mixtures of polyphenolic substances. So far as is known all of said tannins contain at least one aromatic (e.g., benzene) ring having at least one phenolic hydroxyl group attached thereto. Said hydroxyl groups have their hydrogen atoms replaced in alkaline solution. It is believed the hydroxyl groups furnish at least a portion of the reactive sites for complexing an atom of a metal such as iron with the tannin molecule. The reactive sites remaining on the aromatic ring structure are susceptible to sulfoalkylation to add side chain(s) to the tannin molecule.

Due to the complex nature and chemistry of the tannin compounds it is not intended to limit the invention to the above or to any specific reaction mechanism, or to any specific method for preparing the additives of the invention. However, said additives of the invention can be conveniently described in terms of processes for their manufacture. One reaction mechanism by which the product additives of the invention can be formed is as follows. Two reactions, which can be carried out simultaneously or in any order, are involved, (1) a metal complexing reaction whereby an atom of the metal involved complexes with one, two, or three tannin molecules, and (2) a sulfoalkylation reaction whereby the tannin molecule is alkylated by one or more sulfoalkylene radicals attached to said tannin molecule as side chains. The alkylene portion of said sulfoalkylene radical is a methylene or substituted methylene group. Thus, said side chain(s) can be represented by the formulaC(R) -SO M wherein each R is selected from the group consisting of a hydrogen atom and alkyl, cycloalkyl, aryl, and alkaryl radicals, and M is ammonium or an alkali metal depending upon the particular sulfite employed. As indicated hereinafter, it is preferred when R is other than hydrogen, that said R be an alkyl group containing from 1 to 5 carbon atoms.

As indicated above, the reactions involved in the preparation of the additives of the invention are carried out in an alkaline aqueous medium. Hydroxides of the alkali metals sodium, potassium, lithium, rubidium, and cesium can be used to make said medium alkaline. The amounts of said hydroxides used can be varied over a wide range. The principal function of said hydroxide is to impart sufficient initial solubility to the raw tannin so that it can react with the sulfite and aldehyde or ketone reactatns and the metal compound in the sulfoalkylation and metal complexing reactions. In order to obtain practical reaction rates for said reactions, the pH of the reaction medium should be about 10. In any event, enough of the hydroxide is used to make the initial pH of the reaction medium at least 7, and preferably 10 to 13. However, large excesses of the hydroxide above the amount required to initially solubilize the raw tannin should be avoided for best results. After the tannin has been sulfoalkylated it is not necessary that the reaction medium be alkaline. Depending upon the particular metal compound used to supply the complexing metal, the final reaction mixture can have a pH of less than 7. When sulfurous acid and a bisulfite is used as the sulfur compound, sufficient hydroxide should be present to convert these to the sulfite form. If desired, the alkali metal hydroxide can be prereacted with the tannin prior to the addition of the other reactants to the reaction medium.

Carbonyl compounds which can be used in the practice of the invention include any aldehyde or ketone containing a C=O group, the carbon atom of which is capable of becoming a methylene or substituted methylene group. Thus, aldehydes and ketones which can be used can be represented by the formula (R) C=O wherein R is as defined above. Since said R is nonfunctional in the reaction, there is not real limit on what it is or the number of carbon atoms which it contains. However, when R is unduly large, solubility problems in the aqueous reaction medium and also in connection with the solubility of the reaction product are encountered. The larger R groups tend to make the product hydrophobic. In general, this is undesirable when the products are used as the additives in the drilling fluids of the invention. Thus, since it is preferred to carry out the reaction in an aqueous medium,

it is preferred as a practical matter that when R is not hydrogen, it is an alkyl group containing from 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.

Examples of said preferred aldehydes and ketone include:

Formaldehyde Acetaldehyde Propionaldehyde n-Butyraldehyde Isobutyraldehyde n-Valeraldehyde Acetone Methyl ethyl ketone Diethyl ketone Methyl n-propyl ketone Methyl isopropyl ketone.

The sulfur compound used in the practice of the invention is, in general, sulfurous acid and its water-soluble salts such as the alkali metal salts and including the ammonium salts. The alkali metal (as defined above) sulfites are preferred. It is pointed out that when a bisulfite or sulfurous acid is added to the alkaline reaction medium, it will be converted to a sulfite. Therefore, herein and in the claims, unless otherwise designated, the term sulfite is employed generically to include suifurous acid and bisulfites which, when added to the alkaline reaction medium, will be converted to and react as sulfites.

The amounts of the above-described reactants which are used are not critical. So long as a significant amount of each of said reactants is present, the desired reactions will proceed to some extent and some yield of metal complex of sulfoalkylated tannin will be obtained. The amounts of each reactant used will depend upon the amount, the kind of tannin, and the percentage of conversion of said tannin which is desired. For results approaching the optimum, it is preferred to use amounts of said reactants which are within the range of from 0.5 to 1.5 times the stoichiometric equivalent amount of'each reactant which is required to completely react the tannin. Amounts of said reactants which are less than stoichiometric result in less than 100 percent conversion. Amounts in excess of stoichiometric results in a waste of material. Thus, it is preferred to use substantially stoichiometric equivalent amounts of said reactants. For example, the amount of sulfite and aldehyde or ketone is preferably the stoichiometric equivalent amount required in the sulfoalkylation reaction. When the aldehyde or ketone and the sulfite are prereacted, they are preferably prereacted in stoichiomtric equivalent amounts. The amount of the iron or other metal compound used is preferably an amount which is stoichiometrically equivalent to that required to completely complex the tannin.

From the above it is seen that specific numeral ranges ,for the amounts of said reactants will be of only limited Reagent Broad Preferred range, lbs. range, lbs.

Alkali metal hydroxide 60 15 to 30 Sulfite t 20 to 70 Aldehyde or Ketone to 30 Complexiug Metalz Fe to 26 C11,Zn 18 to 40 Cr, Ni, Co, Mn, Ti, and V. 0 to 28 All above metals 9 to 46 1 Calculated as the metal.

However, the ranges set forth in the following Table IA are presently more preferred. TABLE IA.-AMOUNTS OF REAGENTS PER 100 LBS. OF

TANNIN Broad Preferred Preferred range Reagent range, lbs. range, lbs. for qulebracho,

Alkali metal hydroxide.-. 5 to 60 12 to 18 Sulfite 4 to 11 35 to G5 Aldhyde or ketone 1 to 60 to do Complexing metalz Fe 1 to 56..-.. 10 to 26...... G to 20. 1.5to G4 5to 21. l. 5 to 65 7 to 22. 0.8 to 5 8 to 17. 1 t0 5 5 to 20. l to 5 to 19. 1 to (J to 18. 0.8 to 3 to 16. 0. 0 to 8 to 17. 0. 3 to 3 to 9. 0. 3 to 3 to 22.

1 Calculated as the metal.

The above preferred amounts of reactants can be stated in other ways. For example, in working with the amounts shown in the above Table LA, the preferred amount of metal complexing agent (calculated as the metal) to be added to the sulfoalkylated tannin is in the range of from to 3, preferably & to 1, more preferably to mols of metal per monomer mol of active ingredient in the particular tannin compound being used. In other words, it is preferred that no excess metal be present in the reaction mixture at the conclusion of the metal complexing reaction. For example, when quebracho extract is the tannin being used, quebracho catechin is considered to be the active ingredient of the quebracho. Based on a molecular weight of 274 for said quebracho catechin, pounds of quebracho extract will contain an average of 0.33 pound mol of quebracho catechin, and the preferred range of reagents given in column 3 of the above Table I-A has been established on this basis. When other tannin materials are used, the molecular weight of the active ingredient thereof, as well as the amount contained per 100 pounds of tannin, may be different. Thus, it is desirable that the quantities of reagents to be used be established for each particular tannin material used. Those skilled in the art will have no difiiculty establishing the amounts of reagents to use in view of this disclosure. Any large deviation from the 0.33 mol of active ingredient in any individual lot of quebracho extract would also require an adjustment of the chemicals used for reacting with said quebracho. However, analyses of six commercially available quebracho extracts available from different sources has shown that commercial quebracho extract is surprisingly uniform in composition.

The amount of carbonyl compound, e.g., formaldehyde, and the amount of sulfite compound, e.g., sodium bisulfite, used in the reaction will determine the amount of sulfoalkylation of the tannin compound which occurs. This afiords another way of expressing the amount of carbonyl compound and sulfite. The amount of sulfoalkylation which occurs in any given reaction situation can be expressed in terms of the parts by weight of the carbonyl compound-sulfite addition product or sulfoalkylation reagent, e.g., NaSO CH OI-I, formed by reacting stoichiometric amounts of formaldehyde and sodium bisulfite, used per 200 parts by weight of tannin. For example, expressed in this manner and when using formaldehyde, sodium bisulfite, and quebracho, the most preferred amounts of sodium formaldehyde bisulfite addition product will be within the range of from 50 to parts by weight of the sulfomethylation reagent per 200 parts by weight of quebracho.

In general, the reaction conditions are not critical. All the reactions involved in the practice of the invention will take place at ordinary room temperatures (7080 F.) but at a reduced rate and all reaction conditions at which the reactions will take place are within the scope of the invention. However, as a practical matter, it is preferred to employ elevated temperatures to cause said reactions to take place in less time. Any suitable temperature below the decomposition temperature of the tannin can be employed. For example, the application of heat aids in dissolving quebracho in the alkaline medium. As a general rule, temperatures in the order of 125 to 212 F. are sufficient. However, usually a more preferred range is from 180 to 212 F. If desired, the reaction mixture can be refluxed at atmospheric pressure, or can be heated in an autoclave under superatmospheric pressure to obtain higher temperatures. In general, the maximum temperatures employed will be in the order of 300 F. Thus, an over-all numerical range for the reaction temperatures can be said to be from 70 to 300 F.

The reaction time will be dependent upon the reaction temperature employed. Reaction times in the order of 0.5 to 10 hours have been found quite sufficient. Preferably, the reaction times will be within the range of l to 6, more preferably 1 to 4, hours.

The amount of the metal complex additives of the invention used in drilling fluids in accordance with the invention will vary from well to well depending upon conditions encountered in the drilling of the well, the characteristics of the particular drilling fluid being used, the formations being drilled, etc. For example, as the drilling of the well progresses and the well becomes deeper and temperatures in the well increase, or the drilling fiuid becomes contaminated, more additive will usually be required because of said increased temperatures and/or contamination. While therefore the amount of additive used is not of the essence of the invention, it can be stated that the amount of said additive used will normally be within the range of 0.1 to 30, preferably 0.1 to 15, and more preferably 1 to 15, pounds per barrel of drilling fluid. However, it is within the scope of the invention to employ amounts of the additive which are outside said ranges. For example, the amount of additive used will always be an amount which is sufficient to reduce the water loss due to filtration and/or effect an improvement or reduction in the rheological properties of the drilling fluid such as a decrease in yield point, IO-minute gel, or shear strength. As used herein and in the claims, unless otherwise specified, the word barrel refers to a barrel of 42 standard US. gallons.

The following examples will serve to further illustrate the invention. In the following examples the additives of the invention were tested in several different base muds. These base muds were all prepared in conventional manner. In general, the method of preparation of said base muds comprised preparing said muds in five-gallon batches in a suitable blending mill such as a Lear Blend-A Mill. The prepared muds were stirred for at least 30 minutes or more and then aged for three days or more prior to use. The compositions of said base muds are set forth in the following examples and/or in the tables setting forth the results of said examples. In these examples sulfomethylated quebracho is sometimes referred to as SMQ, for convenience. Similarly, the metal complex additives of the invention are sometimes referred to as SMQ-metal complexes. For example, the iron complex of sulfomethylated quebracho is referred to as SMQ-Fe, the copper complex as SMQ-Cu, etc.

EXAMPLE I An iron complex of sulfomethylated quebracho was prepared as follows: 200 grams of ground commercial quebracho extract (11.9 wt. percent water), 500 ml. of water, and 100 ml. of sodium hydroxide (0.5 g. NaOH per ml.) were placed in a beaker and heated to a temperture of about 190 F. to dissolve said quebracho. A second solution was prepared by mixing 104 grams of sodium bisulfite, 89.3 ml. of 36 percent formaldehyde solution, and 500 ml. of water in a separate beaker. The latter solution was mixed and allowed to react for approximately 30 minutes using no external heat source. Said two solutions were then mixed and maintained at a temperature of approximately 160 F. for about 1.5 hours. The resulting solution was then drum dried to recover a sulfomethylated quebracho product.

Freshly precipitated iron hydroxide was prepared by dissolving 7.6 grams of FeCl -6H O in water and precipitating said hydroxide by the additional of ammonia. The precipitate was filtered and washed. A solution of said sulfomethylated queb'racho product was prepared by dissolving 20 grams of same in water. Said precipitated ferric hydroxide was then added to the sulfomethylated quebracho solution, and the resulting solution was heated and maintained at a temperature of about 160 F. for 1.5 hours. The solution was then dried on a hot plate under a heat lamp. The dry product, an iron complex of snlfomethylated quebracho, was then ground.

EXAMPLE II Another i'ron complex of sulfomethylated quebracho was prepared as follows: 233 grams of ground com-mercial quebracho extract (11.9 wt. percent water), 500 ml. of water, and 100 ml. of sodium hydroxide solution (0.5 g. NaOH per ml.) were mixed in a first beaker and heated for one hour with stirring at a temperature of 190 F. in order to dissolve the quebracho and form a first solution. A second solution was formed by adding 208 grams of sodium bisuifite and 178.6 ml. of 36 percent formaldehyde solution to 750 ml. of water. The mixture was al lowed to react for 45 minutes, using no external heat source. Said second solution was then added to said first solution and the combined solution was heated on a hot plate for about 4 hours during which time the temperature was increased from 122 F. to 211 F.

Freshly precipitated ferric hydroxide was prepared by dissolving 135.15 grams of FeCl -6H O in 2.5 liters of water and precipitating said hydroxide by adding 150 m1. of concentrated ammonia solution. The resulting precipitate was filtered and washed, and then added to said com bined first and second solutions. The resulting mixture was heated with stirring for 2.5 hours at a temperature of about l190 F. and the iron hydroxide precipitate was taken into solution. The resulting solution was then evaporated on a drum drier to recover the dry product, an iron complex of sulfomethylated quebracho.

EXAMPLE III A base mud having a composition of 50 pounds of Mc- Cracken clay per barrel of water was prepared in conventional manner. Samples of said base mud containing 4 and 8 pounds per barrel respectively of the iron com plex of sulfomethylated quebracho product of Example I per barrel of said mud were prepared for tests. A second set of samples of said base mud containing 4 and 8 pounds per barrel respectively of the iron complex of sulfomethylated quebracho product of Example II were also prepared for tests. API Code RP-13B properties were then determined on each of said samples with a Model 35 Fann V-G multi-speed viscosimeter and filter presses. The procedure for determination of AP'I Code RIP-13B properties employing the Fann V-G viscosimeter is described by Chisholm and Kohen, Petroleum Engineer, 26 (4), B-87 to B90 (April 1954). The results of said tests are set forth in Table II below.

TABLE II.ADDIIIVES IN BASE MUD NO. 1

[50 lbsJbbl. McCracken clay in water] Run No.

Base Mud 1 2 3 Additive:

A*l= Iron complex of sulfomethylated quebraeho prepared in amp 0 13* Iron complex of sulfomethylated quebraeho prepared in ample II.

EXAMPLE IV Another iron complex of sulfomethylated quebracho was prepared as follows: 200 grams of ground commercial quebracho extract (11.9 weight percent water), 500 ml. of water, and ml. of sodium hydroxide (0.5 g. NaOH per ml.) were placed in a beaker and heated for 1.5 hours at a temperature of about 200 F. to dissolve said quebracho. Another solution was prepared by mixing 104 grams of sodium bisulfite, 89.3 ml. of 36 percent formaldehyde solution, and 500 ml. of water in a separate beaker, and allowing the mixture to react for 30 minutes at room temperature. Said two solutions were then mixed and heated for 3 hours at 205 F.

Freshly precipitated iron hydroxide was prepared by dissolving 50 grams of FeCl -6H O in water and precipitating said hydroxide by the addition of concentrated ammonia solution. The resulting precipitate was filtered and washed, and then added to the above-combined first and second solutions. The resulting mixture was heated,

1 1 with stirring, for two hours at a temperature of 200- 205 F. and the iron hydroxide precipitate was taken into solution. The resulting solution was then evaporated on a drum dried to recover the dry product, an iron comconditions employed in preparing said additives are set forth in Table V below. All of said additives were prepared in the same general manner. Generally speaking, the method of preparation was as follows. The indicated plex of sulfomethylated quebracho. amount of water was added to a suitably-sized reaction X A vessel. The indicated weight of sulfomethylatmg agent was E V then added to said water and was dissolved without the Almse mud hijlvlng a composltloltof Welght Percent addition of external heat. In preparing samples A and B kaol1n and 4 we ght percent bentonite in water Was Pr6- the sodium bisulfite and formaldehyde were added sepap Conventlonal manflefsampls f said base mud rately in the amounts indicated. In the remaining samples, con mmg 3 nd 6 p n p r barrel p ly f the stoichiometric amounts of formaldehyde and sodium bi- Sulfomethylated quebracho p f 0f EXample I W sulfite were prereacted as described elsewhere herein and P p tests- Samples of Salfil base mud qontalnlng then added to the water. The indicated volume of sodium 3 and 6 Pounds P barrel respectively Of the Iron hydroxide solution (0.5 gram per milliliter) was then add- P of sulfomethylated quebracho P Oduct 9 Example ed to the solution with stirring. Heating was initiated and IV were also prepared for tests. Samples of a d base m d the ground quebracho in the amount indicated was added Fontalnlng 3 and 6 Pounds P barrel respectlvely 0f the gradually with stirring, and the addition of heat. The averlrOIl Complex of sulfomethylated q a ho product of age temperature maintained and the reaction time are Example I were also prepared for tests. shown under the heading sulfomethylation reaction. The All of said samples were then tested for API Code 29 metal complexing agent(s), if used, was then added to propernes in accordance with the procedure employed in the hot solution either dry or in solution as indicated in Example III. The results of said tests are given in Table said Table V. III below, Another larger scale batch of SMQ-Fe was also pre- TABLE III.-ADDIIIVES IN BASE MUD NO. 2

[20 wt. percent Kaolin and 4% bentonite in water] Rnn N 0.

Base 1 2 3 4 5 6 7 8 Mud Additive:

B*,1bs./bb1.mud 0 3 0 0 0 0 0 0 0 13*, 1bs./bbl. mud 0 0 0 3 e 0 0 0 0 o*,1bs./bb1.mud 0 0 0 0 0 3 6 0 0 Quebracho 0 0 O 0 0 0 0 3 6 Initial Properties:

Plastic viscosity, cps 1s 14 12 17 19 16 14 19 20 Yield point, lbs/100 it? 14 3 5 6 7 8 9 8 7 Initial gel strength, lbs/100 it. 3 2 2 1 3 4 5 3 3 IO-min. gel strength, lbs/100 it. 23 3 3 6 7 16 16 12 7 pH 9.1 9.1 9.1 7.4 8.4 7.9 8.0 8.9 9.0 Water loss, ml. in min 10.0 7.0 5.0 6.0 4.4 9.2 10.2 8.4 7.6

B*=Iron complex of sulfomethylated quebracho prepared in Example I. D*=Iron complex of sulfomethylated quebracho prepared in Example IV O*=Sulf0methylated quebracho prepared in Example I.

EXAMPLE VI pared. This batch is identified in Table V below as Sam- Base mud No. 3 was prepared from base mud N0. 2 53 E B f t i galions f Wa was of Example V by adding 5 Pounds per barrel of gypsum ble eblad 5 on z g an i a thereto, as a contaminant. Samples of said base mud No. h a F F t f g t pgrcent formalde' 3 containing 3 and 6 pounds per barrel respectively of the 3 t so l i ,i f gun S was i sulfomethylated quebracho product of Example I were Sal e ai so 23 g surfed and prepared for tests. Samples of said base mud containing g s 0 9 Z l a ereio a 3 and 6 pounds per barrel respectively of the iron compeno approxlma e y mmutes' Dunng thls Penod plex of sulfomethylated quebracho product of Example IV were also prepared for tests. Samples of said base mud No. 3 containing 3 and 6 pounds per barrel respectively of the iron complex of sulfomethylated quebracho product of Example I were also prepared for tests.

Each of said samples was then tested for pH and water loss values (API Code 29 procedure). The results of said tests are set forth in Table IV below.

TABLE IV.-ADDITIVES IN BASE MUD NO. 3

the temperature of the solution increased from about v F. to about F. After the reaction between the sodium bisulfite and formaldehyde had been completed, as evidenced by a constant temperature, approximately 35 gallons of a 50 weight percent sodium hydroxide solution was added. The temperature of the solution increased further to about F. At this time 2250 pounds of quebracho were added slowly over a period of approxi- {20 wt. percent kaolin and 4 wt. percent bentonite in water plus 5 lbs. per bbl. of gypsum contaminant] Additives B, D, and 0 same as in Table II.

EXAMPLE VII A series of additives in accordance with the invention mately 20 to 25 minutes. During this rlme the temperature increased to about 200 F. and the temperature was was prepared. The amounts of reagents used and reaction 75 maintained within the range of to 200 F. for approximately 2 hours. The tank contents were vigorously agitated during the addition of the quebracho. At this time 1600 pounds of Ferrifloc (a commercial ferric sulfate) were added slowly over a period of approximately 2 hours with the temperature remaining Within the range of about 190 to about 200 F. After addition of the Ferrifloc was complete the tank contents were circulated for approximately one hour and then passed to a drum drier for recovery of the reaction product, i.e., an iron complex of sulfomethylated quebracho (SMQFe).

The above-described samples of metal complexes of sulfomethylated quebracho were then used in preparing samples of drilling mud by adding various quantities of said additives to one or more of base mud Nos. 4 to 7. These drilling mud samples containing the additives of the invention were all prepared in conventional manner. API Code 29 properties were then determined on said drilling mud samples in the same manner as described in Example III above. Shear strength tests were also run employing a Baroid high temperature aging cell or bomb. Briefly, this, test comprises placing a sample of the mud to be evaluated in the test cell or bomb, closing the bomb, and placing same in a hot oil bath or hot air oven maintained at a uniform temperature. After the desired period of aging at the desired temperature, the bomb is cooled to a temperature below 150 F. and opened. A shear tube, made from stainless steel, is placed on the surface of the sample and suificient gram Weights, if necessary, are placed on the tube to start its downward motion. Unless too much weight has been placed on the tube, it will stop its downward motion at the point where the shear strentgh of the gelled sample against the surface of the tube is suflicient to support the applied Weight. The length of the tube exposed above the sample is then measured. The shear strength in pounds per 100 square feet is obtained from a nomograph by utilizing the force, in grams, applied to the shear tube and the length of exposed tube after the tube reaches equilibrium. Further details .of said test can be obtained from Apparatus and Procedure for the Field Testing of Drilling Muds, pp. 900- and 900-26, Baroid Division, National Lead Co., PO. Box 1675, Houston, Tex. See also Measuring and Interpreting High Temperature Shear of Drilling Fluids, Watkins and Nelson, vol. 198, pp. 213-218, Petroleum Transactions, AIME (1953).

The composition of said base muds, said drilling mud samples, and the results of tests thereon are set forth in Tables VI and VII below. In Table VII tests on comparative drilling mud samples containing commercially available additives of the prior art are also set forth for comparative purposes.

TABLE V.-PREPARATION SUMMARY: SULFOMETHYLATED QUEBRACI-IO AND METAL COMPLEXES THEREOF Sulfomethylation Metal salt Vol. of Moles Metal Sam- Vol. Weight Weight Vol. 37% Vol. Weight Reaction Metal per ple H O NfiSOsCHzOH NaHSOa HCHO NaOH Quebraeho Salt Monomer Mol No. (1111.) (grams) (grams) (1111.) (1111.) (grams) Time, Avg. Weight Solu- Quebracho HL: Temp. Spec1es (grams) tzlon Min F.) (ml) A 320 116 83 200 4:00 189 Al(NO3)3-9H;O--.. B 120 600 4:32 181 Ferrifloe 40 200 3:18 187 Alz(SO4)3-18H20- 40 200 3:55 189 V105 40 200 2:05 185 M11SO4-H2O 40 200 3:08 185 COSO47H2O 40 200 2:11 185 NISOs-GHzO 40 200 2:54 185 C12(SO4)3-5Hz0..- 40 200 2:54 192 011804451120. 40 200 2:54 185 ZnSO4-7Hr0 40 200 4:02 185 TiC14.. a 600 4:10 189 CuSO See paragraph 2 of Example VII for details.

n 60 grams of solid NaOH added. Milliliters.

o Added in two portions, 40 ml. after the NaSO3CH;OH was added and 100 m1. after the metal salt solutions.

TABLE VI.ADDITIVES IN BASE MUD NO. 4 [20 wt. percent kaolin and 4 wt. percent bentonite vyatfi, plus sufiicient barites to give mud weight of 12.2 s. ga

Run Number Base 1 2 3 4 5 6 7 8 9 l0 Mud SMQ-Cu SMQ-Zn SMQ-Mn SMQ-Co SMQ-Ni Additive:

Sample No. (Table V) H H I I D D E E F F Lbs./bbl. mud 0 2. 5 5.0 2. 5 5. 0 2. 5 5.0 2. 6 5. 0 2. 5 5.0 Initial Properties:

Plastic viscosity, cps 25 24 27 22 25 25 27 25 25 24 25 Yield point, lbs/100 ft. 33 4 4 2 1 3 6 4 4 4 5 Initial gel lbs /100 It 2 29 2 3 1 1 2 3 1 2 3 3 e1 3 4 2 2 2 4 7 8 13 11 pH 8.4 9. 1 9.0 9.3 9.3 9.1 9.0 9. 5 9.2 9.1 9.1 After Aging 3 days at 3 Plastic viscosity, cps.-. 28 34 25 26 25 23 24 29 29 25 24 Yield point, lbs/10015 35 4 6 9 6 6 5 13 8 24 4 Initial gel, lbs/ ft.* 16 2 2 3 3 3 2 3 3 3 2 lo-min. gel, lbs/100 it]... 63 3 7 27 12 13 13 32 19 14 4 Water loss, m1./30 min- 10. 2 10.0 10.0 9. 8 10. 2 11.6 11.0 9. 8 9. 8 10.6 10.2 pH 8. 2 8.6 8. 5 85. 8. 4 8. 3 8.2 8.5 8. 6 8. 5 8. 6 Shear Strength, lbs/100 it. 800 170 160 165 145 340 280 90 15 16 TABLE VI.-ADDITIVES IN BA'SE MUD NO. 4Continucd Run Number ase SMQ-Cr SMQ-V SMQ-Al SMQ-Fe SMQ-Ti SMQ- SMQ, Mud v Fe-Cr Fe-Cr Additive:

Sample No. (Table V) G G C C B B .l' N LbSJbbl. mud 2. 5. 0 2. 5 5.0 10.0 2.5 5.0 2. 5 1O Initial Properties:

Plastic viscosity, cps 23 33 25 24 36 27 33 36 43 55 35 Yield point, lbs /100 ft 2 6 4 3 5 10 4 13 10 17 19 21 Initial gel, lbs/100 fti- 1 2 3 3 5 1 3 3 10 3 34 IO-min. gel, lbs/100 ftl. 8 6 3 5 10 2 9 9 50 7 76 pH 9. 2 9.2 9.4 9. 6 8.8 9.1 9.4 9.8 9. 2 9.2 8.1

(Aged at After Aging 3 days at 350 F.: 405 F.)

Plastic visocisty, cps 26 26 29 3O 34 23 24 34 63 61 33 Yield point, lbs/100 111. 6 2 6 7 4 7 4 19 17 21 72 Initial gel, lbs/100 tt. 2 1 3 3 3 2 2 14 4 5 79 10-min. gel, lbs/100 ft. 7 3 3 4 4 18 5 60 10 14 137 Water loss, ml./30 min- 9. 8 9. 2 9.6 8. 8 a 8.0 10.8 9. 8 9. 8 b 7. 0 v 4. 5 11. 1 pH 8.5 8.4 8.5 8.5 8.5 8.4 7.4 8.4 8.3 8.5 8.1 Shear Strength, lbs/100 it 150 21 340 320 60 165 150 590 300 250 470 Commercial product. B Initial water loss was 2.6. b Initial water loss was 7.3. 0 Initial water loss was 6.2. 4 Initial water loss was 9.5. a For Runs 19 and 20.

TABLE VII.ADDITIVES IN BASE MUD NO. 5

[6 wt. percent ventonite in water] Run Number llalase 1 2 3 4 5 6 7 8 9 10 SMQ, SMQ-Fe SMQ-Cu SMQ-Al Q- Quebracho Broxiu Additive:

Sample No. (Table V)..- L M M K K B-l B-l Lbs./bbl. mud 0 5 5 10 5 10 1 5 2. 5 5 Initial Properties:

Plastic viscosity, cps-.. 21 18 18 16 17 14 18 16 21 19 Yield point, lbS./100 it 51 31 4 3 6 12 4 34 35 Initial gel, lbs/100 ftfi..- 36 21 3 2 2 4 2 17 17 19 10-min. gel, lbS./100 ft. 82 26 4 9 3 8 3 3 16 pH 9. 5 9 4 l0. 0 9. 3 9. 3 9. 6 9. 5 9. 3 10. 0 9. 3 9. 2 After Aging 3 days 350 F.:

Plastic viscosity, cps 26 14 11 11 13 12 10 9 16 1G 18 Yield point, lbs/10011:. 47 5 2 1 3 3 2 1 5 4 5 Initial gel, lbs/100 it. 12 2 1 1 3 2 1 3 2 2 1 10 mm. gel, lbS./100 13. 3 1 1 3 3 1 3 2 2 1 Water 1055, InL/BO min. 11. 2 10. 2 10. 4 7. 4 8. 8 7. 8 10. 4 10. 2 12. 0 9. 8 9. 4 pH 8. 4 8. 5 8. 8 8. 3 8. 4 8.1 8. 3 8. 3 8. 5 8. 5 8. 4 Shear Strength, lbs/100 it. 380 360 120 67 105 70 21 18 150 210 650 Referring to Table VI, the results of tests on ten SMQ- metal complex additives of the invention are set forth. These results indicate one of the outstanding properties of the additives of the invention. The data show that all of said additives are highly effective dispersing or thinning agents for drilling muds. The results obtained when said drilling mud samples were aged for three days at 350 F. are particularly outstanding since this represents a very severe test of the gelation characteristics of the drilling fluid. The remarkably lower yield point, 10- minute gel, and shear strength values obtained on the samples containing the additives of the invention, as compared to the values on the aged base mud, show that the additives of the invention are remarkably effective in protecting the drilling mud from high temperature gelation as encountered in high temperature deep wells.

Referring to Table VII, the results there set forth show that the SMQ-metal complex additives of the invention are superior to either SMQ alone, the commercially available thinning agent Q-Broxin, or quebracho.

The metal complexes of sulfoalkylated tannin of the invention can be used in a wide variety of aqueous drilling fluids, e.g., water 'base drilling fluids and oil-in-water emulsion drilling fluids. Further details regarding the use of said metal complexes in drilling fluids, the composition of, and components used in said drilling fluids can be found in said copending application Ser. No. 491,837, filed Sept. 30, 1965, now Patent No. 334,406.

An important advantage of the metal complex additives of the invention is the ease with which they can be dispersed in Water or in the water phase of the drilling fluid. Said metal complexes can be incorporated in the drilling fluids by merely adding same to a stream of the circulating diilling fluid. Said metal complexes are easily pulverized solids which can be added directly as such to the jet hopper commonly employed in formulating drilling fluids. The incorporation of said metal com plexes into the drilling fluid can be either before or during the drilling of the well. Thus, said metal complexes of the invention can be incorporated in the drilling fluid in any suitable manner.

While certain embodiments of the invention have been described for illustrative purposes, the invention obviously is not limited thereto. Various other modifications will be apparent to those skilled in the art in view of this disclosure. Such modifications are within the spirit and scope of the invention.

I claim:

1. A metal complex of a sulfoalkylated tannin, said metal being selected from the group consisting of iron, copper, chromium, nickel, cobalt, manganese, zinc, aluminum, titanium, vanadium, and mixtures thereof.

2. A metal complex of a sulfoalkylated tannin as defined in claim 1, said metal complex having been prepared by the inter-reaction, in an alkaline aqueous reaction medium under reaction conditions, between a tannin compound, a carbonyl compound selected from the group consisting of aldehydes and ketones. a sulfur compound selected from the group consisting of sulfurous acid and water-soluble salts thereof, and a metal compound selected from the group consisting of the hydroxides and the water-soluble salts of iron, copper, chromium, nickel, cobalt, manganese, zinc, aluminum, titanium, vanadium, and mixtures thereof.

3. A metal complex of a sulfoalkylated tannin as defined in claim 1, said metal complex having been prepared by the inter-reaction between a tannin compound selected from the group consisting of the gallotannins and the flavotannins, in an alkaline aqueous reaction medium at a temperature within the range of from 70 to 300 F. and in amounts based on 100 parts by weight of said tannin compound, from 1 to 60 parts by weight of a carbonyl compound selected from the group consisting of the lower molecular weight aldehydes and ketones, from 4 to 115 parts by weight of a sulfur compound selected from the group consisting of sulfurous acid and water-soluble salts thereof, and from 0.3 to 64 parts by weight of a metal selected from the group consisting of iron, copper, chromium, nickel, cobalt, manganese, zinc, aluminum, titanium, vanadium, and mixtures thereof, said metal being present in a compound selected from the group consisting of the hydroxides and the water-soluble salts of said metals.

4. A metal complex of a sulfoalkylated tannin as defined in claim 3 wherein said metal is iron and the parts by weight thereof is within the range of from 6 to 20, said tannin compound is quebracho extract, said carbonyl compound is formaldehyde and the parts by weight thereof is within the range of from to 36, said sulfur compound is sodium bisulfite and the parts by weight thereof is within the range of from 35 to 65, and said metal complex is prepared by reacting said quebracho extract with said formaldehyde and said sodium bisulfite to form sulfomethylaed quebracho, and said iron compound is reacted with said sulfomethylated quebracho to form an iron complex of sulfomethylated quebracho.

5. A metal complex of a sulfoalkylated tannin as defined in claim 3 wherein said metal is copper and the parts by weight thereof is within the range of from 6.5 to 21, said tannin compound is quebracho extract, said carbonyl compound is formaldehyde and the parts by weight thereof is within the range of from 15 to 36, said sulfur compound is sodium bisulfite and the parts by weight thereof is within the range of from 35 to 65, and said metal complex is prepared by reacting said quebracho extract with said formaldehyde and said sodium bisulfite to form sulfomethylated quebracho, and said copper compound is reacted with said sulfomethylated quebracho to form a copper complex of sulfomethylated quebracho.

6. A metal complex of a sulfoalkylated tannin as defined in claim 3 wherein said metal is chromium and the parts by weight thereof is within the range of from 5.8 to 17, said tannin compound is quebracho extract, said carbonyl compound is formaldehyde and the parts by weight thereof is within the range of from 15 to 36, said sulfur compound is sodium bisulfite and the parts by weight thereof is within the range of from 35 to 65, and said metal complex is prepared by reacting said quebracho extract with said formaldehyde and said sodium bisulfite to form sulfomethylated quebracho, and said chromium compound is reacted with said sulfomethylated quebracho to form a chromium complex of sulfomethylated quebracho.

7. A metal complex of a sulfoalkylated tannin as defined in claim 3 wherein said metal is aluminum and the parts by weight thereof is within the range of from 3 to 9, said tannin compound is quebracho extract, said carbonyl compound is formaldehyde and the parts by weight thereof is within the range of from 15 to 36, said sulfur compound is sodium bisulfite and the parts by weight thereof is within the range of from 35 to 65, and said metal complex is prepared by reacting said quebracho extract with said formaldehyde and said sodium bisulfite to form sulfomethylated quebracho, and said aluminum compound is reacted with said sulfomethylated quebracho to form an aluminum complex of sulfomethylated quebracho.

8. A metal complex of a sulfoalkylated tannin as defined in claim 3 wherein said metal is zinc and the parts by weight thereof is within the range of from 6.7 to 22, said tannin compound is quebracho extract, said carbonyl compound is formaldehyde and the parts by Weight thereof is within the range of from 15 to 36, said sulfur compound is sodium bisulfite and the parts by weight thereof is within the range of from 35 to 65, and said metal complex is prepared by reacting said quebracho extract with said formaldehyde and said sodium bisulfite to form sulfomethylated quebracho, and said zinc compound is reacted with said sulfomethylated qubracho to form a zinc complex of sulfomethylated quebracho.

9. A process for preparing a metal complex as defined in claim 1, which process comprises: inter-reacting, in an alkaline aqueous reaction medium under reaction conditions, a tannin compound, a carbonyl compound selected from the group consisting of aldehydes and ketones, a sulfur compound selected from the group consisting of sulfurous acid and water-soluble salts thereof, and a metal compound selected from the group consisting of the hydroxides and water-soluble salts of iron, copper, chromium, nickel, cobalt, manganese, zinc, aluminum, titanium, vanadium, and mixtures thereof; and recovering said metal complex from the resulting reaction medium.

10. A process in accordance with claim 9 wherein: said tannin compound is a gallotannin or a flavotannin; said aldehyde or ketone is a lower molecular weight compound; said inter-reacting of said reagents is carried out at a temperature within the range of from 70 to 300 F; and the amounts of said reagents, based on parts by weight of said tannin compound, are form 1 to 60 parts by weight of said carbonyl compound, from 4 to parts by weight of said sulfur compound, and a suflicient amount of at least one of said metal compounds to supply from 0.3 to 64 parts by weight of at least one of said metals calculated as metal.

11. A process in accordance with claim 10 wherein: said tannin compound is reacted with said carbonyl compound and said surfur compound to form sulfoalkylated tannin; and said metal compound is reacted with said sulfoalkylated tannin to form said metal complex.

12. A process in accordance with claim 11 wherein: said carbonyl compound and said sulfur compound are prereacted in an aqueous medium to form a sulfoalkylation reagent; said aqueous medium is then made alkaline; said tannin compound is then added to said alkaline medium and reacted with said sulfoalkylation reagent to form a sulfoalkylated tannin; and said metal compound is then added to said alkaline medium and reacted with said sulfoalkylated tannin to form said metal complex.

13. A process according to claim 11 wherein said metal is iron and the parts by weight thereof is within the range of from 6 to 20, said tannin compound is quebracho extract, said carbonyl compound is formaldehyde and the parts by weight thereof is within the range of from 15 to 36, said sulfur compound is sodium bisulfite and the parts by weight thereof is within the range of from 35 to 65, and said metal complex is prepared by reacting said quebracho extract with said formaldehyde and said sodium bisulfite to form sulfomethylated quebracho, and said iron compound is reacted with said sulfomethylated quebracho to form an iron complex of sulfomethylated quebracho.

14. A process according to claim 11 wherein said metal is copper and the parts by weight thereof is within the range of from 6.5 .to 21, said tannin compound is quebracho extract, said carbonyl compound is formaldehyde and the parts by weight thereof is within the range of from 15 to 36, said sulfur compound is sodium bisulfite and the parts by weight thereof is within the range from 35 to 65, and said metal complex is prepared by reacting said quebracho extract with said formaldehyde and said sodium bisulfite to form sulfomethylated quebracho, and said copper compound is reacted with said sulfomethylated quebracho to form a copper complex of sulfomethylated quebracho.

15. A process according to claim 11 wherein said metal is chromium and the parts by weight thereof is within the range of from 5.8 to 17, said tannin compound is quebracho extract, said carbonyl compound is formaldehyde and the parts by weight thereof is Within the range of from 15 to 36, said sulfur compound is sodium bisulfite and the parts by Weight thereof is Within the range of from 35 to 65, and said metal complex is prepared by reacting said quebracho extract With said formaldehyde and said sodium bisulfite to form sulfomethylated quebracho, and said chromium compound is reacted with said sulfomethylated quebracho to form a chromium complex of sulfomethylated quebracho.

16. A process according to claim 11 wherein said metal is aluminum and the parts by Weight thereof is Within the range of from 3 to 9, said tannin compound is quebracho extract, said carbonyl compound is formaldehyde and the parts by weight thereof is Within the range of from 15 to 36, said sulfur compound is sodium bisulfite and the parts by Weight thereof is Within the range of from 35 to 65, and said metal complex is prepared by reacting said quebracho extract with said formaldehyde and said sodium bisulfite to form sulfomethylated quebracho, and said aluminum compound is reacted with said sulfomethylated quebracho to form an aluminum complex of sulfomethylated quebracho.

17. A process according to claim 11 wherein said metal is zinc and the parts by Weight thereof is Within the range of from 6.7 to 22, said tannin compound is quebracho extract, said carbonyl compound is formaldehyde and the parts by Weight thereof is Within the range of from 15 to 36, said sulfur compound is sodium bisulfite and the parts by Weight thereof is within the range of from 35 to 65, and said metal complex is prepared by reacting said quebracho extract with said formaldehyde and said sodium bisulfite to form sulfomethylated quebracho, and said zinc compound is reacted with said sulfomethylated quebracho to form a zinc complex of sulfomethylated quebracho.

References Cited UNITED STATES PATENTS 5/1962 Monroe 252-8.5 8/1966 Van Blaricom 260236.5 

